【作者】 王华；

【导师】 吴辉禄；

【作者基本信息】 兰州交通大学 ， 无机化学， 2014， 硕士

【摘要】 香豆素及其衍生物在自然界中广泛存在。由于其有特殊的发光性能所以有许多天然和合成的香豆素衍生物在物理学、生物学、医学和化学等不同的领域获得了应用。因为其突出的光学性质他们也被应用在激光染料、非线性光学生色团、荧光美白产品、荧光探针和太阳能收集器等方面。所以有关该类化合物的研究受到越来越多研究者的关注。苯并咪唑就是一种典型的含氮供体配体，它能与许多过渡金属形成配合物，同时具有良好的生物活性。本文设计合成了2个香豆素双苯并咪唑类配体及8个过渡金属配合物。采用摩尔电导法、元素分析法、红外光谱测量分析法、紫外可见光谱测量分析法和X单晶衍射等手段对得到的配体及其配合物进行了表征。利用紫外滴定光谱、荧光光谱及粘度法对所得到的配体及对应的配合物与DNA的作用方式进行了研究。同时对配体荧光性质也进行了初步的探究。此外，还进行了抗氧化自由基活性的测定，主要针对配体和配合物清除羟基自由基的测定及清除超氧离子自由基的测定。配体简称及配合物化学组成如下：1.6-二（2-苯并咪唑）亚甲基胺香豆素（cbba）为配体的过渡金属配合物[Cd (cbba)2](pic)2·2DMF,(1)2.6-[二（2-苯并咪唑）亚甲基胺]亚甲基香豆素（cbbp）为配体的过渡金属配合物[Cu(cbbp)(Br)(DMF)](pic),(2)[Zn(cbbp)(Cl)2]DMF,(3)[Mn(cbbp)(Cl)2]DMF,(4)[Zn(cbbp)(Br)2]DMF,(5)3.双苯并咪唑亚甲基胺(IDB)为配体的过渡金属配合物[Cu(IDB)2]2(pic)4·3DMF,(6)[Mn(IDB)2](pic)2,(7)[Ni(IDB)2]·2NO2,(8)其中(2)(3)(4)(5)(6)的中心金属原子采取五配位的配位模式，除了配合物(2)(6)以外其他配合物的空间几何结构为三角双锥。(1)(7)(8)中心金属原子采取六配位的配位模式，空间几何结构均为扭曲的八面体。通过对所得到的实验结果进行分析，发现配体及配合物与DNA是以插入的模式键合的。同时也进行了配体对金属离子识别的初步而简单的研究，在乙腈-H2O (9:1, v/v)的缓冲液里配体cbba具有强的荧光，当Cu2+离子加入时会发生荧光淬灭的现象。此外，对抗氧化自由基活性的测定研究结果发现，除了(5)以外配体和配合物具有较强的清除羟基自由基的能力，(2)(4)(6)(7)还具有很好的清除超氧离子自由基的能力。更多还原

【Abstract】 Coumarin and its derivatives occur widely in nature. Many natural and syntheticderivatives of coumarin are used in different applications in chemistry, biology, medicine andphysics, due to their luminescence properties. They are also used in laser dyes, nonlinearoptical chromophores, fluorescent whiteners, fluorescent probes and solar energy collectorsdue to their outstanding optical properties. Therefore, coumarin and its derivatives haveattracted considerable interests in recent years. Moreover, the benzimidazole rings as a typicalheterocyclic ligand can be formed with some main group, transition and rare-earth metalcomplexes, at the same time have good biological activity.In this paper, two ligands and eight transition metal complexes of those ligands weresynthesized. The ligands and metal complexes were measured by molecular conductivities,elemental analysis, IR, UV-Vis spectra and X-ray single crystal diffraction. Interactions of theligands and complexes with DNA were investigated by spectrophotometric methods andviscosity measurements. The fluorescence properties of the ligands were also investigated.Additionally, the antioxidant activity of the ligands and complexes were determined by thesuperoxide and hydroxyl radical scavenging methods in vitro. These complexes are listed asfollow:1.6-[bis(2-benzimidazolylmethyl)amine]coumarine（cbba）and its metal complexes:[Cd (cbba)2](pic)2·2DMF,(1)2.6-[bis(2-benzimidazolylmethyl)aminemethyl]coumarine (cbbp) and its metalcomplexes:[Cu(cbbp)(Br)(DMF)](pic),(2)[Zn(cbbp)(Cl)2]DMF,(3)[Mn(cbbp)(Cl)2]DMF,(4)[Zn(cbbp)(Br)2]DMF,(5)3. bis(2-benzimidazolylmethyl)amine (IDB) and its metal complexes:[Cu(IDB)2]2(pic)4·3DMF,(6)[Mn(IDB)2](pic)2,(7)[Ni(IDB)2]·2NO2,(8)In those complexes,(2)(3)(4)(5)(6) adopted five-coordinated modes, and except for complex(2)(6)the coordination geometry of the central metal atom may be best described as trigonalbipyramidal.(1)(7)(8) adopted six-coordinated modes, and the coordination geometry of thecentral metal atom may be best described as distorted octahedral. The results suggested thatligands and complexes can interaction with DNA in an intercalate mode. Meanwhile, ligandscbba which has a strong fluorescence response shows fluorescence quenching upon addingCu2+in Acetonitrile-H2O buffer (1:9, v/v). Additionally, we undertook a systematic investigation on the antioxidant potential of ligands and complexes and the results indicatedall complexes had stronger ability of antioxidation for hydroxyl radical except complex (5),(2)(4)(6)(7) also has good scavenging activity for superoxide radical.更多还原